CN100482596C - Method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously - Google Patents
Method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously Download PDFInfo
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- CN100482596C CN100482596C CNB2006100981807A CN200610098180A CN100482596C CN 100482596 C CN100482596 C CN 100482596C CN B2006100981807 A CNB2006100981807 A CN B2006100981807A CN 200610098180 A CN200610098180 A CN 200610098180A CN 100482596 C CN100482596 C CN 100482596C
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Abstract
The method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously includes absorbing SO2 and/or fluoride from waste gas with alkaline absorbent to generate desulfurizing and defluorinating absorbent liquid containing sodium sulfite, sodium bisulfite and/or fluoride; the subsequent reacting the desulfurizing and defluorinating absorbent liquid with magnesium-base suspension or solid to obtain magnesium sulfite and/or magnesium fluoride precipitate; filtering to eliminate magnesium sulfite and/or magnesium fluoride precipitate, and recovering the filtrate at pH 6.5-9.5 for reuse. The said method has fast regeneration reaction speed, low cost and complete reaction.
Description
Technical field
The present invention relates to method to fluorine-containing, sulphur-containing exhaust gas defluorinate, the reclaiming of desulfurization absorption liquid.
Background technology
At present, sulfur-bearing, fluorine-containing industrial gaseous waste mainly concentrate in the waste gas of boiler of power plant waste gas, glass melter and glass fibre tank furnace, mainly contain objectionable constituent such as sulfurous gas, fluorochemical in these waste gas, and be bigger to environmental hazard.More to the technical study that removes sulfurous gas both at home and abroad, sweetening agent has single component and two-pack.
The concrete grammar that adopts single component to administer has: one, ammoniacal liquor is made absorption agent: spray absorbs the sulfurous gas in the waste gas, the ammonium bisulfite that generates is used ammonia treatment again, can make ammonium sulphite, the ammonium sulfate by-product is made in oxidation, this method has been done introduction at ZL98117223.7, but this method ammonia is volatile, causes new pollution; Two, calcium alkaline process: as absorption agent, absorb sulfur in smoke with the suspension liquid of lime or calcium hydroxide, generate calcium sulfite, the oxidation by-product gypsum, this method absorption system equipment is huge, and the milk of lime internal circulating load is big, the easy fouling of system is stopped up, but industrial use is still more; Three, soda method: adopt sodium hydroxide or aqueous sodium carbonate as absorption agent, this method equipment is simple, less investment, but alkali consumption is big, and the cost height seldom uses in the production.Four, magnesian lime method: water slurry (13-20%) the absorption sulfur in smoke of employing magnesian lime, this method is owing to use slurries, and storage and conveying are all difficult, and the easy fouling of system is stopped up.
The employing two-pack is administered, and it is made up of desulfurization and desulfurization regeneration two portions.Concrete grammar has: one, with ammonia as sweetening agent, do the desulfurization regeneration agent with calcium hydroxide, this method ZL97103626.8 has again been done introduction, this method ammonia is volatile, causes new pollution, and regenerative response speed is slower; Two, with the magnesium base as sweetening agent, with lime or calcium hydroxide as regenerator, the oxidation calcium sulfite is made by-product gypsum, this method has been done introduction at ZL95104688.8, ZL02146547.9, ZL02806288.4 etc., and this method is because magnesium sulfite solubleness is less, and magnesium sulfite is less in the absorption liquid, make following absorption liquid measure bigger, energy consumption increases, and the calcium hydroxide reproduction speed is slower, and regenerating unit is huge.Byproduct calcium sulfate does not have utility value.Three, with the sodium base as sweetening agent, with lime or calcium hydroxide as regenerator, the oxidation calcium sulfite is made by-product gypsum, and He Zhensheng etc. have done introduction in " glass fibre " 2004 the 3rd phases, and ZL01107106.0 has also done introduction, this method regenerative response time is longer, regenerating unit is huge, and reaction not exclusively causes the consumption alkali number bigger, running cost is higher, lessly uses on the large scale industry device.Four, magnesium sulfite circulation method: adopt the circulation of magnesium sulfite clear liquid to absorb sulfur in smoke, magnesium bisulfite that generates and magnesium hydroxide reaction generate magnesium sulfite, saturated magnesium sulfite clear liquid is got back to absorptive unit, because the solubleness of magnesium sulfite in water is low, the clear liquid internal circulating load is big, the absorption tower is imported and exported absorption liquid PH and is changed greatly, influences assimilated efficiency, and absorptive unit equipment is bigger.
For technology of Fluoride Removal, mainly adopt lime method, basic identical with desulfurization technology.At present, the method of handling the waste gas that glass melter and glass fibre tank furnace produce is mainly sodium calcium method, contains sulfurous gas and fluorochemical etc. in the waste gas, sodium calcium method with the sodium base as sweetening agent, sodium hydroxide and sulfurous gas and fluorochemical reaction generate sulfurous acid Asia and fluorochemical; With lime or calcium hydroxide as regenerator, generate the salt precipitation of calcium sulfite and fluorochemical, regenerated liquid S-WAT and aqueous sodium hydroxide solution go back to absorb sulfurous gas and fluorochemical again, this method regenerative response time is longer, regenerating unit is huge, and reaction is incomplete, and fluorochemical accumulates in circulation fluid, it is bigger to consume alkali number simultaneously, and running cost is higher.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of reaction times short, consume that alkali number is less, that investment, running cost are low is fluorine-containing, the continuous reclaiming method of the absorption liquid of the defluorinate of sulphur-containing exhaust gas, desulfurization.
The object of the present invention is achieved like this:
A kind of fluorine-containing, the desulfurization of sulphur-containing exhaust gas, the continuous reclaiming method of defluorinating absorbent liquid, it be will contain sulfurous gas or/and the waste gas of fluorochemical with the base absorption liquid with the sulfurous gas in the waste gas or/and fluorochemical absorb, generation contains S-WAT, sodium bisulfite is or/and the desulfurization of the sodium salt of fluorochemical, defluorinating absorbent liquid, then, with desulfurization, defluorinating absorbent liquid is Yu Magnesium base suspension or solid reaction, make S-WAT, sodium bisulfite is fluorochemical De Magnesium salt and precipitating or/and the sodium salt of fluorochemical is converted into magnesium sulfite, remove by filter magnesium sulfite or/and the magnesium salts precipitation of fluorochemical, reclaim filtrate, filtrate pH is 6.5-9.5, makes base absorption liquid recirculation and uses.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid, the aqueous solution of the buffer system that the aqueous solution that described base absorption liquid is a S-WAT or S-WAT and sodium bisulfite are formed.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid, described base absorption liquid can repeatedly circulate and absorb sulfurous gas in the waste gas or/and fluorochemical, as the pH of base absorption liquid during, carry out the reclaiming of next step desulfurization, defluorinating absorbent liquid and handle at 4.2-7.5.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid, Suo Shu De Magnesium base suspension or solid are the suspension of magnesium hydroxide, magnesium oxide or magnesiumcarbonate or their solid, or the suspension of their mixture or solid.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid, the quality total content of magnesium hydroxide, magnesium oxide or magnesiumcarbonate is not less than 30% in the described magnesium base suspension.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid, described desulfurization, defluorinating absorbent liquid and magnesium base suspension or solid reaction are at 0-70 ℃, reaction was carried out 10-20 minute.
The continuous reclaiming method of the desulfurization of above-mentioned waste gas, defluorinating absorbent liquid can be used for the defluorinating absorbent liquid of desulfurization absorption liquid, waste gas containing fluoride of sulphur-containing exhaust gas or sulfur-bearing, the desulfurization of waste gas containing fluoride, the continuous reclaiming of defluorinating absorbent liquid.Principle of the present invention is as follows:
The invention has the advantages that 1) regenerative response speed is fast, can effectively reduce the investment and the running cost of reclaim equiment; 2) regenerative response is complete, and regeneration clear liquid PH height can be implemented high PH circulation and absorb, and waste gas absorbs the processing efficiency height.Solved existing sodalime double alkali method calcium sulfur ratio height simultaneously, the problem of mass consumption liquid caustic soda, this law need only be replenished small amount of alkali, the sodium ion amount that magnitude of recruitment is only taken out of for waste residue.3), the solubleness of S-WAT is big in the circulating absorption solution of this law, can implement absorption, the reprocessing cycle of circulation fluid higher concentration, and it is little that the PH variation is imported and exported on the absorption tower, improves assimilated efficiency, reduces absorption equipment investment and operation power consumption; 4) Chinese natural high-content magnesium oxide reserves are big, and use cost is lower than calcium hydroxide, and is solid materials, and transportation stores convenient.5), can effectively avoid forming the slagging scorification of fluorochemical magnesium salts such as magnesium fluoride at absorptive unit for the absorption of fluorochemical.6) throw out magnesium sulfite and fluorochemical magnesium salts have higher comprehensive utilization value.
Description of drawings
Fig. 1 is fluorine-containing, the defluorinate of sulphur-containing exhaust gas of the present invention, the schematic flow sheet of desulfurization recovery method.
Embodiment
Following examples can illustrate the present invention well.
Get the circulating absorption solution 200ml that contains S-WAT, sodium bisulfite and fluorochemical, its pH is 6.5, and fluorinion concentration is 1055mg/l, adds magnesium base suspension (50% magnesium hydroxide) 5g, and temperature of reaction is 10 ℃, and the reaction times is 10 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 8.3, and fluorinion concentration is 151mg/l.
Get the circulating absorption solution 200ml that contains S-WAT, sodium bisulfite and fluorochemical, its pH is 6.5, and fluorinion concentration is 1055mg/l, adds calcium base suspension (50% calcium hydroxide) 8g, and temperature of reaction is 10 ℃, and the reaction times is 10 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 7.1, and fluorinion concentration is 346mg/l.
Get the circulating absorption solution 200ml that contains S-WAT, sodium bisulfite, its pH is 6.0, adds magnesium base suspension (50% magnesium oxide) 4g, and temperature of reaction is 30 ℃, and the reaction times is 15 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 8.4.
Get the circulating absorption solution 200ml that contains S-WAT, sodium bisulfite, its pH is 6.0, adds calcium base suspension (50% calcium hydroxide) 4g, and temperature of reaction is 30 ℃, and the reaction times is 15 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 7.0.
Get the circulating absorption solution 200ml of fluoride sodium salt, its pH is 6.0, and fluorinion concentration is 2050mg/l, adds magnesium base suspension (50% magnesiumcarbonate) 4g, and temperature of reaction is 30 ℃, and the reaction times is 30 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 7.1, and fluorinion concentration is 195mg/l.
Embodiment 4. usefulness magnesium hydroxides are made magnesium base suspension
Get the circulating absorption solution 200ml of the sodium salt that contains S-WAT, sodium bisulfite and fluorochemical, its pH is 7.5, and fluorinion concentration is 1050mg/l, adds magnesium base suspension (50% magnesium hydroxide) 5g, and temperature of reaction is 30 ℃, and the reaction times is 30 minutes.After reaction finished, filtering-depositing, the pH of supernatant liquor were 9.5, and fluorinion concentration is 175mg/l.
As shown in Figure 1, the waste gas that contains sulfurous gas and fluorochemical enters defluorination desulfurization absorptive unit 1 by pipeline 6.Be used to remove the base water absorption liquid of sulfurous gas and fluorochemical, the aqueous solution of sodium hydroxide or yellow soda ash or S-WAT or their mixtures for example, join circulatory pool 2 by pipeline 8, base water absorption liquid enters wet absorption unit 1 by pump 18 through pipeline 9 and spray equipment 21 from circulatory pool 2, with with the air-flow countercurrent flow, sulfurous gas in the waste gas and fluorochemical and the reaction of base component simultaneously, desulfurization defluorination from waste gas, and clean air communication is crossed pipeline 7 from absorptive unit 1 discharging.Base water absorption liquid is converted into the waste liquid that contains S-WAT, sodium bisulfite and Sodium Fluoride, and delivers to circulatory pool 2 by pipeline 19, makes circulated sprinkling and uses.
The part of waste liquid that contains the sodium salt of S-WAT, sodium bisulfite and fluorochemical is discharged from absorptive unit 1, and to pipeline 10, control pH value of aqueous solution this moment is between 4.2-7.5 by valve 20.
To deliver to regenerative response unit 3 from the waste water of pipeline 10.Be used for regenerated magnesium base suspension, the suspension liquid of magnesium hydroxide or magnesiumcarbonate or magnesium oxide or their mixture is added to regenerative response unit 3 by pipeline 11, with waste water reaction from pipeline 10, reaction generates magnesium sulfite and fluorochemical magnesium salts, reactant enters settling tank 4 by pipeline 12, supernatant liquid returns circulatory pool 2 by pipeline 13, precipitation by pipeline 14 install 5 after filtration, pipeline 15 discharges, filtrate is returned circulatory pool 2 with the supernatant liquor of pipeline 13 through pipeline 17 by pipeline 16.
In pipeline 17 returns the aqueous solution of circulatory pool 2, contain S-WAT and sodium bisulfite, this moment pH value of aqueous solution between 6.5-9.5, make circulated sprinkling and use.
The throw out of reaction is magnesium sulfite and fluorochemical magnesium salts, reclaims comprehensive utilization.
This method can be handled and contain form waste gas of sulfur dioxide or fluoride waste gas or contain sulfurous gas and the waste gas of fluorochemical.
The desulfurization of the waste gas that embodiment 6. glass fibre tank furnaces produce, the continuous reclaiming of defluorinating absorbent liquid
The waste gas that glass fibre tank furnace produces, mark attitude air quantity is 35000 cubic metres/hour, sulfur dioxide concentration is 1800 milligrams/cubic metre, fluoride concn is 600 milligrams/cubic metre, the technical process of the continuous reclaiming method of desulfurization, defluorinating absorbent liquid as shown in Figure 1, the waste gas that glass fibre tank furnace produces, through the base absorption liquid absorb the desulfurization behind the compounds such as sulfurous gas in the waste gas and fluorochemical at absorptive unit 1 internal recycle, the pH of defluorinating absorbent liquid is 6.5, fluorinion concentration is 950mg/l, and flow is 40m
3/ h enters regeneration reactor 3, adds the magnesium hydroxide solid simultaneously in its regeneration reactor 3, add-on be 180 kilograms/time, temperature of reaction is 40 ℃, stopping the reaction times is 15 minutes, reaction solution enters settling tank after flocculation, precipitating sludge fully utilizes after press filtration; Supernatant liquid and filtrate are returned into the absorption tower and are absorbed sulfurous gas and fluorochemical as base absorption liquid circulation, and its pH is 8.3, and fluorinion concentration is 221mg/l.
The continuous reclaiming of the desulfurization absorption liquid of the waste gas that embodiment 7. coal firing boilers produce
The waste gas that coal firing boiler produces, mark attitude air quantity be 58500 cubic metres/time, sulfur dioxide concentration is 1680 milligrams/cubic metre, absorptive unit 1 is one-level cooling, one-level eddy flow tower, the technical process of the continuous reclaiming method of desulfurization absorption liquid as shown in Figure 1, tail gas behind the sulfurous gas of waste gas process base absorption liquid in absorption tower internal recycle absorption waste gas that coal firing boiler produces effluxes, the concentration of the sulfurous gas of tail gas is 136 milligrams/cubic metre, processing efficiency is 92%, the desulfurization absorption liquid enters regeneration reactor 3, the pH of its absorption liquid is 6.6, and flow is 60m
3/ h adds magnesium base suspension (30% magnesium oxide) simultaneously in the regeneration reactor 3, flow is 680L/h, and temperature of reaction is 50 ℃, and the reaction times is 20 minutes, and reaction solution enters settling tank 4 after flocculation, and precipitating sludge fully utilizes after installing 5 press filtrations after filtration; Supernatant liquid and filtrate are returned into the absorption tower and are absorbed sulfurous gas as base absorption liquid circulation, and its pH is 8.5.
Claims (7)
- One kind fluorine-containing, the desulfurization of sulphur-containing exhaust gas, the continuous reclaiming method of defluorinating absorbent liquid, it be will contain sulfurous gas or/and the waste gas of fluorochemical with the base absorption liquid with the sulfurous gas in the waste gas or/and fluorochemical absorb, generation contains S-WAT, sodium bisulfite is or/and the desulfurization of the sodium salt of fluorochemical, defluorinating absorbent liquid, it is characterized in that: with desulfurization, defluorinating absorbent liquid is Yu Magnesium base suspension or solid reaction, make S-WAT, sodium bisulfite is fluorochemical De Magnesium salt and precipitating or/and the sodium salt of fluorochemical is converted into magnesium sulfite, remove by filter magnesium sulfite or/and fluorochemical De Magnesium salt precipitation, reclaim filtrate, filtrate pH is 6.5-9.5, makes base absorption liquid recirculation and uses.
- 2. the continuous reclaiming method of the desulfurization of waste gas according to claim 1, defluorinating absorbent liquid is characterized in that: described base absorption liquid is the aqueous solution that contains the buffer system that S-WAT or S-WAT and sodium bisulfite form.
- 3. the continuous reclaiming method of the desulfurization of waste gas according to claim 1, defluorinating absorbent liquid, it is characterized in that: described base absorption liquid can repeatedly circulate and absorb sulfurous gas in the waste gas or/and fluorochemical, as the pH of base absorption liquid during, carry out the reclaiming of next step desulfurization, defluorinating absorbent liquid and handle at 4.2-7.5.
- 4. the continuous reclaiming method of the desulfurization of waste gas according to claim 1, defluorinating absorbent liquid, it is characterized in that: Suo Shu De Magnesium base suspension or solid are the suspension of magnesium hydroxide, magnesium oxide or magnesiumcarbonate or their solid, or the suspension of their mixture or solid.
- 5. the continuous reclaiming method of the desulfurization of waste gas according to claim 4, defluorinating absorbent liquid, it is characterized in that: the quality total content of magnesium hydroxide, magnesium oxide or magnesiumcarbonate is not less than 30% in the described magnesium base suspension.
- 6. the continuous reclaiming method of the desulfurization of waste gas according to claim 1, defluorinating absorbent liquid is characterized in that: described desulfurization, defluorinating absorbent liquid are Yu Magnesium base suspension or solid reaction are at 0-70 ℃, and reaction was carried out 10-20 minute.
- 7. the continuous reclaiming method of the desulfurization of waste gas according to claim 1, defluorinating absorbent liquid is characterized in that: can be used for the defluorinating absorbent liquid of desulfurization absorption liquid, waste gas containing fluoride of sulphur-containing exhaust gas or sulfur-bearing, the desulfurization of waste gas containing fluoride, the continuous reclaiming of defluorinating absorbent liquid.
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| CN102641660B (en) * | 2012-05-09 | 2014-09-03 | 四川省川宏精细化工有限公司 | Recycling method of fluorine in fluorophlogopite process gas |
| CN106039969A (en) * | 2016-07-21 | 2016-10-26 | 黄立维 | Sulfur dioxide absorption method and device |
| CN106861432B (en) * | 2017-03-31 | 2020-02-07 | 湖南求是检测科技有限公司 | Purification process of renewable desulfurization absorption liquid |
| CN106890505A (en) * | 2017-04-14 | 2017-06-27 | 哈尔滨理工大学 | A kind of double alkali method desulfurizing system filters intermediate processing |
| CN114804396B (en) * | 2021-01-28 | 2023-04-07 | 无锡中天固废处置有限公司 | High-salinity lye pool wastewater treatment process |
| CN115090096A (en) * | 2022-06-06 | 2022-09-23 | 武汉天源环保股份有限公司 | Landfill leachate deodorization method and system |
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| 石灰乳吸收法处理轮窑烧砖烟气的研究. 陈凡植等.广东工学院学报，第13卷第1期. 1996 |
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Application publication date: 20070606 Assignee: Lianhui Resources and Environmental Protection Co., Ltd. Assignor: Lu Yongkai|Qiu Tao Contract record no.: 2010320000183 Denomination of invention: Method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously Granted publication date: 20090429 License type: Exclusive License Record date: 20100308 |